EP0636848A1 - Schmelzverfahren von elektroleitenden Materialien in einem Induktionsschmelzofen mit kaltem Tiegel und Ofen dafür - Google Patents

Schmelzverfahren von elektroleitenden Materialien in einem Induktionsschmelzofen mit kaltem Tiegel und Ofen dafür Download PDF

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Publication number
EP0636848A1
EP0636848A1 EP94401703A EP94401703A EP0636848A1 EP 0636848 A1 EP0636848 A1 EP 0636848A1 EP 94401703 A EP94401703 A EP 94401703A EP 94401703 A EP94401703 A EP 94401703A EP 0636848 A1 EP0636848 A1 EP 0636848A1
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EP
European Patent Office
Prior art keywords
electroconductive material
electromagnetic
jet
liquid
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94401703A
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English (en)
French (fr)
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EP0636848B1 (de
Inventor
Pascal Colpo
Jean Driole
Sylvain Witzke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TECPHY
Original Assignee
Imphy SA
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Publication date
Application filed by Imphy SA filed Critical Imphy SA
Publication of EP0636848A1 publication Critical patent/EP0636848A1/de
Application granted granted Critical
Publication of EP0636848B1 publication Critical patent/EP0636848B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00Crucible or pot furnaces
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00Crucible or pot furnaces
    • F27B14/06Crucible or pot furnaces heated electrically, e.g. induction crucible furnaces with or without any other source of heat
    • F27B14/061Induction furnaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10Supplying or treating molten metal
    • B22D11/11Treating the molten metal
    • B22D11/114Treating the molten metal by using agitating or vibrating means
    • B22D11/115Treating the molten metal by using agitating or vibrating means by using magnetic fields
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D39/00Equipment for supplying molten metal in rations
    • B22D39/003Equipment for supplying molten metal in rations using electromagnetic field
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00Heating by electric, magnetic or electromagnetic fields
    • H05B6/02Induction heating
    • H05B6/34Arrangements for circulation of melts
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2213/00Aspects relating both to resistive heating and to induction heating, covered by H05B3/00 and H05B6/00
    • H05B2213/02Stirring of melted material in melting furnaces

Definitions

  • the present invention relates to a method of melting an electroconductive material in a melting furnace by induction in a cold crucible and a melting furnace for the implementation of this method.
  • This process is generally used to carry out a stabilized casting of a molten metal with a variable casting rate for the production of metallic powders by atomization.
  • induction melting furnaces are known in which a crucible intended to receive an electroconductive material is used and which is called a cold crucible because it is constantly cooled.
  • partial or total melting of a mass of the liquid electroconductive material is caused by electromagnetic confinement so as to separate the mass of said liquid electroconductive material from the wall of the crucible.
  • the crucible is composed of several metal sectors electrically isolated from each other and surrounded by a means of heating by electromagnetic induction of the electroconductive material contained in said crucible.
  • the crucible is for example of cylindrical shape comprising a substantially hemispherical bottom or conical provided with a pouring orifice to which is fixed a pouring tube of the mass of the liquid electroconductive material.
  • Induction melting furnaces with a metallic cold crucible are preferred over refractory crucible furnaces which pollute the mass of liquid electroconductive material by contact of said material with the refractory walls of the crucible.
  • the pollution is due to the formation of inclusionary particles of, for example, oxidized compounds.
  • this pollution incorporates into the powders numerous inclusions and it is in particular recognized that the presence of such inclusions in rotating parts of aeronautical engine, for example based on nickel, can be the cause of defects in service performance of these parts subjected to fatigue stresses and in particular lead to premature ruptures of parts subjected to high stresses at high temperature.
  • Such a nozzle has the drawback of being conditioned, in its operation, by the choice of specific dimension parameters, as well as parameters for defining the magnetic field applied such as for example the frequency and intensity of said magnetic field.
  • this nozzle has a large footprint and a low efficiency.
  • This centripetal movement at the upper surface of the molten charge allows the materials not yet perfectly melted floating on the surface of the charge, to be brought to the center and then to be engulfed in this charge, and therefore allows mixing of the mass of molten material without taking account of the inclusions present in said mass fondue.
  • two phenomena are used which are an electromagnetic stirring making it possible to bring within the molten metal mass the inclusions towards the electromagnetic skin area and a capture of the inclusions in the skin area, said inclusions being offset towards the wall of the crucible and the surface of the molten metal mass under the effect of magnetic pressure forces.
  • the object of the invention is to propose a method of melting an electroconductive material in a melting furnace by induction in a cold crucible which makes it possible to ensure dynamic purification by volume of the mass of the liquid electroconductive material before and during casting, by settling of inclusions.
  • At least two superimposed vortices are created in the mass of molten electroconductive material subjected to electromagnetic stirring.
  • the invention also relates to a melting furnace of an electrically conductive material by induction in a cold crucible, for the implementation of the process mentioned above, said melting furnace comprising a crucible intended to contain said electrically conductive material and formed of several metal sectors electrically isolated from each other, means for cooling the metal sectors, means for heating by electromagnetic induction of the electroconductive material arranged around the crucible, a pouring tube of the liquid electroconductive material arranged vertically below the crucible and electromagnetic means for confining the jet of liquid electroconductive material in the pouring tube, said electromagnetic means being arranged around the pouring tube and supplied by a generator, characterized in that it comprises means for centering electromagnetic means for confining the jet of mast riau liquid electroconductive with respect to the vertical axis of the pouring tube and the crucible and means for centering and positioning the crucible sectors with respect to the means of electromagnetic induction heating of the electroconductive material and with respect to the electromagnetic means for confining the jet liquid electroconductive material.
  • Fig. 1 there is shown schematically a melting furnace 10 by induction in a cold crucible intended in particular for the purification of a mass 1 of an electroconductive material before its atomization for the manufacture of powders.
  • the melting furnace 10 comprises a crucible 11 intended to contain the electroconductive material 1 and formed of several metal sectors 12 electrically insulated from each other and each provided with a means of cooling by circulation of water not shown in FIG. 1.
  • the number of metal sectors 12 is by example of new.
  • the crucible 11 is for example of cylindrical shape extending by a substantially hemispherical or conical bottom provided with an orifice 13 for pouring the mass of the electroconductive material 1 liquid.
  • the melting furnace 10 also includes means 14 for electromagnetic induction heating of the electroconductive material 1 arranged around the crucible 10.
  • These means 14 of heating by electromagnetic induction are composed for example of eight turns.
  • the melting furnace 10 also comprises a pouring tube 15 of the liquid electroconductive material 1 arranged vertically below the crucible 11 and in the axis of the pouring orifice 13 and means 16 for confining the jet of liquid electroconductive material 1 in said pouring tube 15.
  • the electromagnetic means 16 for confining the jet of liquid electroconductive material are arranged around the pouring tube 15 and supplied by a generator not shown in the figures.
  • the pouring tube 15 is formed of eight cylinder sectors 15a cooled by a circuit 17 for circulation of a fluid such as for example water.
  • the means 16 for confining the jet of liquid electroconductive material 1 in the pouring tube 15 are formed by an extra-flat electromagnetic coil 16, such as for example a BITTER coil, comprising for example ten turns 16a in the form of copper plates, distributed over a height of 30mm, for a jet of electroconductive material of approximately 12mm in diameter.
  • an extra-flat electromagnetic coil 16 such as for example a BITTER coil, comprising for example ten turns 16a in the form of copper plates, distributed over a height of 30mm, for a jet of electroconductive material of approximately 12mm in diameter.
  • Each of the copper plates is pierced with thirty-six 2.5mm diameter holes connected to a circuit 18 for transverse water circulation for cooling the electromagnetic coil 16.
  • the melting furnace 10 comprises means 20 for centering the electromagnetic coil 16 for confining the jet of liquid electroconductive material relative to the vertical axis of the pouring tube 15 and of the crucible 11 and means 25 for centering and positioning of the sectors 12 of the crucible 11 relative to the means 14 of electromagnetic induction heating of the electroconductive material 1 and relative to the electromagnetic coil 16.
  • the means for centering the electromagnetic coil 16 are formed by an envelope 20 made of an insulating material, for example of PERMAGLAS, inserting the turns 16a of said electromagnetic coil 16.
  • the means for centering and positioning the sectors 12 of the crucible 11 are formed by a shell 25 made of an insulating material, for example of PERMAGLAS, disposed around said sector 12 and inserting the means 14 for electromagnetic induction heating of the electroconductive material 1 and the cooling means sectors 12.
  • This coating makes it possible to maintain the turns of the means 14 for induction heating of the electroconductive material 1 and the crucible 11 which avoids hydrodynamic disturbances in the mass of liquid electroconductive material.
  • the induction furnace 1 comprising the crucible 11 and the pouring tube 15 can be placed in an enclosure under controlled atmosphere and the material flow jet electroconductive is subjected to bursting for shaping the powder.
  • the perfect vertical cylindrical geometry of the casting jet of the electroconductive material is an important, even essential, characteristic of the good quality of the powders obtained by atomization.
  • the mass of electroconductive material 1 constituted by a superalloy steel with a radius of 5 cm is placed in the crucible 11 and the power transmitted by the means 14 of heating by electromagnetic induction and of the order of 50 KW for a current of 1000 A at a frequency of 20KHz.
  • the Applicant has found that the non-conductive particles, contained in the mass of electroconductive material 1 to be treated, were subjected, in an electromagnetic vortex medium, to a series of forces such as drag force, virtual mass, Archimedes thrust , hydrodynamic pressure, force of lorentz which made it possible to deduce the behavior of the inclusions in a particular electromagnetic stirring.
  • the Applicant has determined a configuration that is most favorable for the separation of the non-conductive inclusionary particles contained in the mass of the molten and confined electroconductive material and for their decantation at the surface of this mass.
  • the method according to the invention consists, during electromagnetic stirring, in creating in the mass of the electrically conductive material 1 liquid at least one vortex 30 in which the solid or liquid inclusion particles are entrained in a vortex movement in a spiral and decanted when they reach the surface of this mass of the electrically conductive material 1.
  • This coaxial alignment requires that the electromagnetic coil 16 of the means for confining the jet generates an electromagnetic field in cylindrical symmetry with the vertical axis of the melting furnace 10.
  • a conventional spiral coil with a conductor of circular tubular section cannot be suitable for confining the casting jet, because each of the turns forms a current path which moves in a plane inclined relative to the vertical axis , directly dependent on the pitch of the propeller of the electromagnetic coil.
  • a conventional electromagnetic coil generates a magnetic field creating instabilities of casting the jet.
  • the means for confining the pouring jet of the mass of the electroconductive material are formed by an extra-flat electromagnetic coil 16 of the type described above.
  • the electromagnetic field generated by the electromagnetic coil 16 is determined so that the magnetic pressure jump is maximum, for a given power of the generator supplying said electromagnetic coil 16.
  • Fig. 3 there is shown schematically, the movement of the mass of the liquid electroconductive material 1 which is materialized by the two superimposed vortices 30 whose displacement speed is approximately 0.2 m / s.
  • Figs. 4 and 5 represent two diagrams materializing the displacement of the nonconductive inclusionary particles respectively in the upper vortex and in the lower vortex.
  • the solid inclusionary particles are decanted as soon as they reach the surface of the mass of the liquid electroconductive material 1, without taking into account the mechanism for capturing these particles around the free surfaces or a cold wall, by phenomena interfacial like magnetic pressure.
  • Measuring the settling time makes it possible to control the minimum time for melting the mass of the electroconductive material and for mixing this mass which ensures the purification by settling of the inclusionary particles of given size.
  • the separation time of the inclusion particles is maximum for the particles initially located near the center of the vortex (s) 30 and the settling time is very important for the small inclusion particles.
  • the Applicant has found that the efficiency of the electromagnetic confinement of the casting jet of the mass of the electroconductive material 1 is all the greater the higher the magnetic pressure jump between the axis and the surface of the casting jet. .
  • the pressure jump is a function of the electromagnetic force applied and the depth of penetration of the magnetic field into the casting jet.
  • Fig. 6 shows three curves showing the variation of the value of the pressure jump ⁇ Pm as a function of the ratio of the radius R of the casting jet to the penetration depth ⁇ of the magnetic field, for different electrical resistivities ⁇ of the electroconductive material.
  • the method according to the invention allows, thanks to the electromagnetic confinement of the pouring jet associated with the coaxiality of the magnetic fields of the means for confining the pouring jet, means of induction heating of the mass of the electroconductive material, the crucible and said mass of the electroconductive material to obtain a control of the electromagnetic stirring of this liquid mass, while ensuring the continuous separation of the solid inclusion impurities contained in the electroconductive material while also making it possible to obtain an improved quality of the products.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • General Engineering & Computer Science (AREA)
  • Crucibles And Fluidized-Bed Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Furnace Details (AREA)
EP94401703A 1993-07-29 1994-07-25 Schmelzverfahren von elektroleitenden Materialien in einem Induktionsschmelzofen mit kaltem Tiegel und Ofen dafür Expired - Lifetime EP0636848B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9309366 1993-07-29
FR9309366A FR2708725B1 (fr) 1993-07-29 1993-07-29 Procédé de fusion d'un matériau électroconducteur dans un four de fusion par induction en creuset froid et four de fusion pour la mise en Óoeuvre de ce procédé.

Publications (2)

Publication Number Publication Date
EP0636848A1 true EP0636848A1 (de) 1995-02-01
EP0636848B1 EP0636848B1 (de) 1998-09-30

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EP94401703A Expired - Lifetime EP0636848B1 (de) 1993-07-29 1994-07-25 Schmelzverfahren von elektroleitenden Materialien in einem Induktionsschmelzofen mit kaltem Tiegel und Ofen dafür

Country Status (7)

Country Link
US (1) US5563904A (de)
EP (1) EP0636848B1 (de)
JP (1) JP3696903B2 (de)
KR (1) KR950003779A (de)
CA (1) CA2128936C (de)
DE (1) DE69413621T2 (de)
FR (1) FR2708725B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013183031A1 (en) * 2012-06-08 2013-12-12 Imp Automation (Pty) Ltd Separating system and method
CN109253622A (zh) * 2018-08-03 2019-01-22 荆门它山之石电子科技有限公司 一种制备含微孔的铝合金的熔炼炉

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GB9600895D0 (en) * 1996-01-17 1996-03-20 Coutts Duncan R Improved method and apparatus for melting a particulate material
US5809057A (en) * 1996-09-11 1998-09-15 General Electric Company Electroslag apparatus and guide
IT1289001B1 (it) * 1996-10-14 1998-09-25 Danieli Off Mecc Sistema per l'agitazione elettromagnetica del metallo liquido in forni elettrici ad arco a corrente continua
FR2766497B1 (fr) * 1997-07-25 2001-05-11 Cogema Elaboration et tirage en continu, en creusets froids inductifs, de metaux ou d'alliages
US6104742A (en) * 1997-12-23 2000-08-15 General Electric Company Electroslag apparatus and guide
US6097750A (en) * 1997-12-31 2000-08-01 General Electric Company Electroslag refining hearth
US6221123B1 (en) 1998-01-22 2001-04-24 Donsco Incorporated Process and apparatus for melting metal
US6144690A (en) * 1999-03-18 2000-11-07 Kabushiki Kaishi Kobe Seiko Sho Melting method using cold crucible induction melting apparatus
US6219372B1 (en) * 1999-12-29 2001-04-17 General Electric Company Guide tube structure for flux concentration
EP1514065B1 (de) * 2002-06-15 2007-04-25 Solios Thermal Limited Elektromagnetisches induktionsgerät und verfahren zur behandlung geschmolzener werkstoffe
RU2224966C1 (ru) * 2002-08-05 2004-02-27 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ электромагнитного перемешивания электропроводного расплава и устройство для его осуществления
TWI265198B (en) 2002-12-02 2006-11-01 Univ Nat Taiwan The method and equipments for controlling the solidification of alloys in induction melting using cold crucible
US20060291529A1 (en) * 2005-05-26 2006-12-28 Haun Robert E Cold wall induction nozzle
KR101218923B1 (ko) * 2010-09-15 2013-01-04 한국수력원자력 주식회사 유도코일과 용융로 일체형 유도가열식 저온용융로
RU2543022C1 (ru) * 2013-11-11 2015-02-27 Общество с ограниченной ответственностью "Научно-производственный центр магнитной гидродинамики" Печь-миксер
JP6146319B2 (ja) * 2014-01-17 2017-06-14 トヨタ自動車株式会社 金属溶融装置
US10898949B2 (en) 2017-05-05 2021-01-26 Glassy Metals Llc Techniques and apparatus for electromagnetically stirring a melt material
RU189343U1 (ru) * 2018-09-27 2019-05-22 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" Устройство магнитогидродинамического перемешивания жидкого металла в цилиндрической ванне
WO2020071944A1 (ru) * 2018-10-05 2020-04-09 Общество с ограниченной ответственностью "Диотон" Способ перемешивания расплава металла и электромагнитный перемешиватель для его реализации (варианты)
RU207347U1 (ru) * 2021-07-23 2021-10-25 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования «Новосибирский Государственный Технический Университет» Устройство магнитогидродинамического перемешивания жидкого металла в цилиндрической ванне
KR20230055789A (ko) * 2021-10-19 2023-04-26 주식회사 제이피에스 마이크로 웨이브의 선택적 조사를 통한 용융물의 히팅이 가능한 로 시스템
CN117628900B (zh) * 2024-01-22 2024-03-29 中信戴卡股份有限公司 一种铝合金再生用三室熔化炉

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DE1583445A1 (de) * 1967-11-21 1970-08-13 Demag Elektrometallurgie Gmbh Elektrischer Induktionsofen
FR2316026A1 (fr) 1975-07-04 1977-01-28 Anvar Dispositif electromagnetique de confinement des metaux liquides
FR2396612A2 (fr) 1977-07-08 1979-02-02 Anvar Dispositif electromagnetique de confinement des metaux liquides pour realiser une regulation de debit
FR2397251A1 (fr) 1977-07-12 1979-02-09 Anvar Procede et dispositif pour diriger, en l'absence de parois, des veines metalliques liquides, notamment pour les centrer, les guider ou controler leur forme circulaire
EP0005676A2 (de) * 1978-05-23 1979-11-28 C E M COMPAGNIE ELECTRO MECANIQUE Société Anonyme Elektromagnetisches Rührverfahren beim Stranggiessen
EP0021889A1 (de) * 1979-05-31 1981-01-07 ANVAR Agence Nationale de Valorisation de la Recherche Verfahren zum Einschnüren flüssiger Metallströme durch Anwendung eines elektromagnetischen Feldes
FR2646858A1 (fr) 1989-05-11 1990-11-16 Snecma Procede de refusion de materiaux metalliques avec decantation inclusionnaire
EP0408453A1 (de) * 1989-07-12 1991-01-16 Societe Nationale D'etude Et De Construction De Moteurs D'aviation "Snecma" Vorrichtung für eine elektromagnetische Giessdüse zum Regeln eines Flüssigmetallstrahles
FR2665249A1 (fr) 1990-07-26 1992-01-31 Dauphine Ets Bonmartin Laminoi Four de fusion par induction en creuset froid.

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EP0260617B1 (de) * 1986-09-16 1991-12-04 Centrem S.A. Verfahren und Vorrichtung zur Herstellung und Weiterverarbeitung metallischer Stoffe
US5102449A (en) * 1989-05-11 1992-04-07 Societe Nationale D'etude Et De Construction De Moteurs D'aviation "S.N.E.C.M.A." Inclusion decanting process for nickel-based superalloys and other metallic materials

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Publication number Priority date Publication date Assignee Title
DE1583445A1 (de) * 1967-11-21 1970-08-13 Demag Elektrometallurgie Gmbh Elektrischer Induktionsofen
FR2316026A1 (fr) 1975-07-04 1977-01-28 Anvar Dispositif electromagnetique de confinement des metaux liquides
FR2396612A2 (fr) 1977-07-08 1979-02-02 Anvar Dispositif electromagnetique de confinement des metaux liquides pour realiser une regulation de debit
FR2397251A1 (fr) 1977-07-12 1979-02-09 Anvar Procede et dispositif pour diriger, en l'absence de parois, des veines metalliques liquides, notamment pour les centrer, les guider ou controler leur forme circulaire
EP0005676A2 (de) * 1978-05-23 1979-11-28 C E M COMPAGNIE ELECTRO MECANIQUE Société Anonyme Elektromagnetisches Rührverfahren beim Stranggiessen
EP0021889A1 (de) * 1979-05-31 1981-01-07 ANVAR Agence Nationale de Valorisation de la Recherche Verfahren zum Einschnüren flüssiger Metallströme durch Anwendung eines elektromagnetischen Feldes
FR2646858A1 (fr) 1989-05-11 1990-11-16 Snecma Procede de refusion de materiaux metalliques avec decantation inclusionnaire
EP0408453A1 (de) * 1989-07-12 1991-01-16 Societe Nationale D'etude Et De Construction De Moteurs D'aviation "Snecma" Vorrichtung für eine elektromagnetische Giessdüse zum Regeln eines Flüssigmetallstrahles
FR2649625A1 (fr) 1989-07-12 1991-01-18 Snecma Dispositif de busette electromagnetique pour le controle d'un jet de metal liquide
FR2665249A1 (fr) 1990-07-26 1992-01-31 Dauphine Ets Bonmartin Laminoi Four de fusion par induction en creuset froid.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013183031A1 (en) * 2012-06-08 2013-12-12 Imp Automation (Pty) Ltd Separating system and method
CN109253622A (zh) * 2018-08-03 2019-01-22 荆门它山之石电子科技有限公司 一种制备含微孔的铝合金的熔炼炉

Also Published As

Publication number Publication date
FR2708725B1 (fr) 1995-11-10
FR2708725A1 (fr) 1995-02-10
DE69413621D1 (de) 1998-11-05
US5563904A (en) 1996-10-08
EP0636848B1 (de) 1998-09-30
CA2128936C (fr) 2004-06-22
CA2128936A1 (fr) 1995-01-30
JP3696903B2 (ja) 2005-09-21
DE69413621T2 (de) 1999-04-29
JPH07207351A (ja) 1995-08-08
KR950003779A (ko) 1995-02-17

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